基于密度泛函理论团簇Co_(4)MoP的催化析氢研究  

The Study on Catalytic Hydrogen Evolution of Co_(4)MoP Clusters Based on Density Functional Theory

作　　者：吴庭慧 方志刚[1] WU Tinghui;FANG Zhigang(School of Chemical Engineering,University of Science and Technology Liaoning,Anshan Liaoning 114051,China)

机构地区：[1]辽宁科技大学化学工程学院,辽宁鞍山114051

出　　处：《江西师范大学学报(自然科学版)》2024年第6期551-556,共6页Journal of Jiangxi Normal University(Natural Science Edition)

基　　金：国家自然科学基金(51634004);国家级大学生创新创业训练计划(202310146025,202310146026,202310146027,202210146008,202110146027)资助项目.

摘　　要：该文基于密度泛函理论,利用Gaussian16和Multiwfn软件,系统分析了团簇Co_(4)MoP的析氢性能.研究结果表明:团簇Co_(4)MoP存在8种稳定构型,其中构型1^((4))在热力学上最为稳定,显示出最低的吉布斯自由能变化(ΔG=-13869067.14 kJ·mol^(-1)).结合能较高的构型1^((2))和2^((2))在二重态下表现出显著的热力学稳定性,进一步验证了其在析氢反应中的潜在优势.在析氢反应过程中,电子从团簇的HOMO转移到水分子的LUMO,促进氢原子的生成.构型3^((2))在形成Co_(4) MoP-H结构后,其ΔE值最小,为483.613 kJ·mol^(-1),显示出最高的反应活性和电子转移效率.相比之下,构型2^((2))在形成Co_(4)MoP-H结构后的ΔE值最大,解吸氢气的活性最弱.该研究揭示了不同构型在催化析氢反应中的稳定性和反应活性差异,为设计和优化高效的非贵金属HER催化剂提供了理论依据.Based on density functional theory and using Gaussian16 and Multiwfn software,the hydrogen evolution performance of Co_(4)MoP clusters is systematically analyzed in this paper.The results reveal that Co_(4)MoP clusters have eight stable configurations,with configuration 1(4)being the most thermodynamically stable,showing the lowest Gibbs free energy change(ΔG=-13869067.14 kJ·mol^(-1)).Configurations 1^((2))and 2^((2)),with higher binding energies,exhibit significant thermodynamic stability in the doublet state,further verifying their potential advantages in hydrogen evolution reactions.During the hydrogen evolution reaction,electrons transfer from the cluster′s HOMO to the water molecule′s LUMO,promoting hydrogen atom generation.Configuration 3^((2))forms a Co_(4)MoP-H structure with the smallest ΔE value of 483.613 kJ·mol^(-1),indicating the highest reaction activity and electron transfer efficiency.In contrast,configuration 2^((2))forms a Co_(4)MoP-H structure with the largest ΔE value,showing the weakest hydrogen desorption activity.Overall,the differences in stability and reaction activity are highlighted among different configurations in catalyzing hydrogen evolution,providing important theoretical guidance for designing and optimizing efficient non-precious metal HER catalysts.

关 键 词：密度泛函理论 析氢反应 吉布斯自由能变 

分 类 号：O641.12[理学—物理化学]